I. Field of the Invention
This invention relates to the preparation of hydrazones and specifically to the preparation of hydrazones by the method of reacting a primary or secondary amine, ammonia, and a carbonyl compound with a peroxide compound.
II. Description of the Prior Art
From numerous publications it is known that the primary or secondary amines are easily oxidized by peroxide compounds into very diverse oxygenated products, such as hydroxyl amines, nitroso or nitrated derivatives, oximes, compounds having an azoxy function, amides, etc., depending on the particular structure of the reactants or the reaction conditions. Thus, a description has been given of the oxidation of primary aliphatic amines to nitroalkanes by peracetic acid (W. D. Emmons, J. Am. Chem. Soc., 79, 5528, 1957) or other percarboxylic acids (see for example the paper by H. O. Larson in "The Chemistry of the Nitro and Nitroso Groups", part I, p. 309, published by H. Feuer, Interscience, New York, 1969).
The primary aromatic amines have been oxidized into the corresponding nitroso, nitro, or azoxy derivatives by the pure percarboxylic acids or by a mixture of acetic acid and a 30% aqueous solution of hydrogen peroxide (R. R. Holmes and R. P. Bayer, J. Am. Chem. Soc., 82, 3454, 1960; see also the paper by W. M. Weaver in "The Chemistry of the Nitro and Nitroso Groups." part 2, p. 29, published by H. Feuer, Interscience, New York, 1970). Aniline has also been oxidized into azoxybenzene by hydrogen peroxide in the presence of acetonitrile (G. B. Payne, P. H. Deming and P. H. Williams, J. Org. Chem., 26, 659, 1961). The oxidation of secondary amines into the corresponding hydroxyl amines has, for example, been effected by means of diacyl peroxides (French Pat. No. 1,360,030), of hydrogen peroxide in the presence of formic acid esters (German Pat. No. 1,004,191), or of hydrogen peroxide in the presence of nitriles (F. C. Schaefer and W. D. Zimmermann, J. Org. Chem., 35, 2165, 1970).
In previous patents and applications for patents the applicants have moreover described new processes for the synthesis of azines by oxidation of ammonia in the presence of a carbonyl compound (III) with one of the peroxide compounds mentioned above, in accordance with the general reaction ##EQU2##
The oxidizing agent can be a percarboxylic acid (IV) (pending U.S. application Ser. No. 290,507, filed Sept. 20, 1972), a diacyl peroxide (V) (pending U.S. application Ser. No. 308,836, filed Nov. 22, 1972), hydrogen peroxide in the presence of salts (VI) as catalysts (pending U.S. application Ser. No. 267,921, filed June 30, 1972), hydrogen peroxide in the presence of nitriles (VII) as co-reactants (French Pat. 2,092,734, applied for June 12, 1970, and pending U.S. application Ser. No. 152,413, filed June 11, 1971), hydrogen peroxide in the presence of esters (VII) as co-reactants (pending U.S. application Ser. No. 340,762, filed Mar. 13, 1972), a hydrogen peroxide in the presence of amides or imides (IX) as co-reactants (pending U.S. application Ser. No. 341,057, filed Mar. 14, 1972), and hydrogen peroxide in the presence of cyanogen compounds (X) as co-reactants (pending U.S. application Ser. No. 340,762, filed Mar. 13, 1972).